Storing carbon underground can have unintended consequences

From Greenpeace - "FALSE HOPE

One of the key challenges for CCS is the safe and permanent storage of captured carbon. Even very small leakage rates could completely undermine any climate mitigation efforts.

The world has no experience of the long-term storage of anything, let alone CO2.
As the results of a 2006 United States Geological Survey (USGS) field experiment1 show, there is every chance that carbon dioxide will behave in ways that are totally
unexpected. The USGS scientists were testing deep geological disposal of carbon dioxide at a pilot project in Frio, Texas.

The researchers were surprised when the buried CO2 dissolved large amounts of the surrounding minerals responsible for keeping it contained. The CO2 reacted with salty water (brine) in the geological formation turning it as acidic as vinegar. This acidified brine then dissolved other minerals, including metals such as iron and manganese, organic material and relatively large amounts of carbonate materials. Carbonates naturally seal pores and fractures in geological sites; the reaction of the acidic brine with them is extremely concerning. Carbonate is also found in the cements used to plug abandoned oil and gas wells. If these open, CO2 could leak into the atmosphere and/or the contaminated brine could leak into the aquifers that supply drinking and irrigation water.

In an interview with Greenpeace, lead scientist Yousif Kharaka warned that the results are “a cautionary note: for detailed and careful studies of injection sites, and a well thought out monitoring program to detect early study show that we simply do not know enough about how stored carbon will behave to be able to assure its safe and permanent storage.

1 Kharaka Y K, Cole D R, Hovorka S D, Gunter W D, Knauss K G & Freifeld B M, ‘Gas-water-rock interactions in frio formation following CO2 injection:
Implications for the storage of greenhouse gases in sedimentary basins’, Geology, vol., 34, no. 7, 2006, pp. 577–580.
2 Kharka, Yousif, 2007, USGS, Research Hydrologist, Interview conducted over e-mail.

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Research for Deployment: Incorporating Risk, Regulation,and Liability for Carbon Capture and Sequestration

Carbon capture and sequestration (CCS) has the potential to enable deep reductions in global carbon dioxide (CO₂) emissions, however this promise can only be fulfilled with large-scale deployment. For this to happen, CCS must be successfully embedded into a larger legal and regulatory context, and any potential risks must be effectively managed. We developed a list of outstanding research and technical questions driven by the demands of the regulatory and legal systems for the geologic sequestration (GS) component of CCS. We then looked at case studies that bound uncertainty within two of the research themes that emerge. These case studies, on surface leakage from abandoned wells and groundwater quality impacts from metals mobilization, illustrate how research can inform decision makers on issues of policy, regulatory need, and legal considerations. A central challenge is to ensure that the research program supports development of general regulatory and legal frameworks, and also the development of geological, geophysical, geochemical, and modeling methods necessary for effective GS site monitoring and verification (M&V) protocols, as well as mitigation and remediation plans. If large-scale deployment of GS is to occur in a manner that adequately protects human and ecological health and does not discourage private investment, strengthening the scientific underpinnings of regulatory and legal decision-making is crucial.

Potential Groundwater Quality Impacts from Metals Mobilization.

Groundwater merits special attention because it is a precious resource, and it is subject to current regulation. While there are several ways in which large-scale injection or leakage might affect water supplies, most attention has focused on CO₂−brine−rock interactions. While processes in this system could affect both organic and inorganic geochemistry of aquifers, only the mobilization of inorganic compounds, chiefly metals, through dissolution and transport will be considered here.

South Liberty (Frio) Pilot, TX.

In 2004, a DOE pilot field experiment in South Liberty, TX injected 1800 t of CO₂ into the Frio saline formation (29). This injection was designed to validate simulations of CO₂ transport and fate in one of the largest saline formations in the United States. A monitoring well located 100 ft. from the injection well collected direct fluid samples using a U-tube apparatus (30). This tool and others detected arrival of a CO₂ plume in the monitoring well 7 days after injection.

Of note, a substantial amount of dissolved metal was recovered in the U-tube (31). Initially, workers thought that the well casing was reacting to carbonic acid in the reservoir. However, laboratory studies and geochemical analyses confirmed that a substantial fraction of the metals were the product of mineral dissolution, specifically the oxide and hydroxide coatings of mineral grains that represent <2%>31). The rapidity of mobilization and the high concentrations suggested strongly that carbonic acid formed from dissolved CO₂ in formation brines might quickly and dramatically alter groundwater chemistry.

The Frio was the first saline formation analyzed in this way. Ultimately, this result is not unexpected, yet it is not clear whether this effect of metal mobilization is common or significant at depth. It is also not clear what fraction of metals would be transported with CO₂ should it leak to other formations. However, it raised the concern that should CO₂ leak into a shallow freshwater aquifer, there could be consequences that could negatively affect groundwater quality, potentially impacting public health and acceptance of CCS deployment.

Carbonate and Siliclastic Systems.

To a first order, both injection targets and shallow aquifers can be divided into siliciclastic or carbonate systems. This division reflects the primary composition of the reservoir rocks. Carbonate systems chiefly comprise calcite, aragonite, dolomite, and other carbonate minerals that form limestones and dolostones, whereas siliciclastic systems chiefly comprise frag ments of quartz, feldspar, and other siliceous minerals that form sandstones, siltstones, and shales.

This compositional difference greatly affects the response of carbon acid. Silicate minerals react slowly with CO₂, which means that there is little change in porosity and permeability over the duration of injection; however, the brines with dissolved CO₂ will remain acidic. In contrast, carbonate rocks react quickly with CO₂ and could change permeability and porosity quickly; however, the rapid kinetics will result in rapid increase of brine pH and buffering of the brine−CO₂ system, reducing reactivity over time. Because of these competing effects, it is not clear which fundamental rock composition is more prone to leakage or to mobilizations of metals, and little work has focused on direct comparison of these two primary aquifer compositions.

Key U.S. Freshwater Aquifer Settings.

Given the distribution of CO₂ point sources and potential GS reservoirs, it is likely that CO₂ storage will be concentrated in a small number of basins. To understand and appraise the potential for metal mobilization in shallow aquifers, it would be helpful to understand the composition and acid-reaction response near the surface of these basins. Table 2 provides a subset of key shallow aquifers in these basins and some issues around their geology.